Polyurethane foams using esterified dimer acids



United States Patent h 3,173,887 POLYURETHANE FOAMS USTNG ESTERHFIED DIR/[ER ACIDS Thomas E. Yeates and Charles M. Thierfelder, Peoria,

3,173,887 Patented Mar. 16, 1965 Free The dimerized polyunsaturated fatty acid starting material consisting of three parts of C -dibasic acid and one part C -tribasic acid is known (see Young et .21., US. Patent No. 2,491,350) and is commercially available.

5 The general method for condensing the said dimer acid assiguors to me United Sta-fies of America as repmaterial with ethylene oxide in the presence of an alkaline resented by the Secretary of Agriculture N No Drawing. Filed Dec. 19, 1962,Ser.No.245,939 Catalyst 15 also known. See Barker, US. Patent o.

2 Claims. 1 2(} .2.5) 2,758,976, who reacted dimer acid with 28 molar equiv- (Granted under Title 35, U.S. Code (1952), see. 256) alents of ethylene oxide to obtain a viscosity-stabilizing hydraulic fluid additive. However, this prior art highly A n nex irrevocable, y ylicense in the etherified dimer acid material would be completely inll'lVeIllIlOIl herein described, throughout the world 01 all Operative for applicants purpose inasmuch as e were P poses of the United States Government, w $116 POWEr unable to prepare stable polyurethane foams with dimer to grant sublic s r Such P P is hereby granted acid that was reacted with more than 2 molar equivalents to the Government of the United States of America. of ethylene oxide, above which level of reaction some This invention relates to novel polyester int rm diat s etherification takes place and the shrinkage of the foam and to polyester polyurethane foams made therewith. prior to crosslinking became very extensive and could not More particularly, our invention relates to novel polybe materially reduced even by reversing the mixing order. ester-type intermediates that are prepared by hy r xy Table I shows the conditions employed for several hyethylating commercially available dimer-acid to critical droxyethylations f th di id d th principal extents and to inexpensive polyester-type flexible polycharacteristics of the esterified dimer acids. As would be urethane foams prepared therewith. expected, it also shows the marked effect on the viscosity Cost considerations in the highly competitive commcrof the resulting ester of increasing the temperature and cial production of urethane foams have resulted in the inthe reaction time. Table II shows the properties of the creased use of polyether polyols in place of the more exesterified dimer acid starting materials used in procedural pensive polyester polyols. Tables III and IV in which the orders of addition and In an attempt to somewhat offset the loss of markets mixing differ and in Table V which shows the properties for polyunsaturated vegetable drying oils such as soybean of the cured foams. The mixing order indicated in Table and linseed oils and their constituent acids in indoor IV was employed in order to permit polymerization to paints and in polyesterurethane foams, we have now disbegin ahead of the evolution of CO and is preferred to covered that commercially available dimer-acid obtained the mixing order shown in Table III. by dimerizing polyunsaturated vegetable oil fatty acids The following example is intended to more fully dewhen esterified within certain critical molar proportions, scribe the invention. i.e., with from 1 to 2 moles of ethylene oxide per mole of EXAMPLE 1 dimer acid, are suitable as low-cost reactants with con Into a Waxed paper cup were placed 169 g. of hydroxsh venmmal dnsc'cyanaes to q polyester F l foams ethylated dimer acid (dimer acid No. 5 of Table II) conthat cost less conventlonal polyestemrqflfams and taining 1.1 mole equivalents of ethylene oxide and 8 ml. that are characterized by favorably low densities on the of a commercially available mixture consisting of P6? of 2 (to 3 lbsjcu'fi' 49 cent 2,4-tolylene dii-socyanate and 20 percent 2,6-tolylene Thus a Principal i of our invenfign is the P P diisocyanate. After stirring the mixture at 5,900 r.p.m. tion from commercially available dimer acid products of f a f moments, 5 gm. trigthylenediamine Catalyst critically esterified derivatives having adequate functiondi l d i 025 y Water was added and the mixture ality as Well as Viscosities in thfi range of about 3500- stirred as before, thus generating a foam which cured by 13,000 cps. which we found on reaction with isocyanate t di overnight at 70 Q The properties f this to be essential for successful foam formation and entrap- 9) and several replicate foams (Nos. 10-12) are shown ment as well as for the avoidance of shrinkage. i T bl Table I .-H ydroxyethylation of dimer acid Reaction conditions Product characterstios a Time, hr. Q 79151 3 B t zi g C i 3533 S3532. n b

pulses -158 0. 5 36 183 1. 1 141-161 1 62 110 -155 1 63 as 1-75 1.8 -153 3 es 101 140-177 0 790 54 184 1. 1 203-210 0 900 59 180 1. 4 192-253 3 1, 500 24 1.24 c 1.1 -230 0 2, 200 50 B The low acid values, even with les resulted from p Moles ethylene oxide] mole dimer acid as calculated from saponification values.

K 00 catalyst was used for these experiments; NaOCHa for the others.

Table II..Analyses of hydroxyethylated dimer acid 41 We claim: 1. The product obtained by esterifying a polyunsatufiydmxyethylatfed dime-T acid starting rated vegetable oil derived dimer acid mixture comprising material numbers Analysis r three parts of C -d1bas1c acid and one part of C -tr1basic 1 2 3 l 4 5 acid with from 1 to not more than about 2 mole equivalents of ethylene oxide, said product having an acid num- Adidvalne; 16 0 [1 0j 055 Hydmxy mine-u 55 113 P 138 fig ber of 0-16, a saponi catlon number of 172-183, and a S'aponification va1ue 180 176 72 a i Moles ethylgne Oxide/mole 1 1 1 7 2 1 1 I; 1 1O viscoslty at 25 C. ofbetween 36 and 132 polses.

dimeraoi 1. f viscosityat C poiswn 90 132 112 79 39 2. Polyes-e1 urethane foams obtained by rapidly min 111g gg g gfigggfl 886 797 about from 35.4 to 61-.() parts by weight of ltolylenednso- Fiseher),wt. percent 0.03 cyanate, about from 0.3 to 1.7 parts by Weight of tri'ethw ylenediamine catalyst, about from 1.5 to 3.9 parts by I Table HI Foams epared one shot technique weight of Water, and 100 parts by weight of dimer acid FoamNos that has been esterified with from 1 to not more than Formula about 2 mole equivalents of ethylene oxide, saiddimer 7 8 acid comprising 3 parts of polyunsaturatedvegetable oil derived C -dibasic acid and 1 part of similarly derived 0'1 0'2 2% C -tribasic acid, the oxyethylenated dimer acid reactant H 1 0.5 1.0 Pgwoxyethymed Vegetable on (an 2 5 5 being characterized by an acid number of 0 16, a sapon e ulsil'er m p V r o m 1 Le Mixed Dagmar Solution r lication number of 172 183, and a viscosity at C. Then added hydroxyethyla'ted' dimer 20 cf between 3 6 and 132 0 5,

' acid, sample No. (of Table II) 2, 3 4 Weight, g 17. 2 32 39. 3 'd t ci't1' 1 d" E g 1 1g V 1500 a 91 O 5 n Then a e o y ene 1 yan Stirred 3 1 11 102mm? began References Cited by the Examiner a out2sec. V 1 36 UNITED STATES PATENTS Table I V.Faams prepared with reversed mixing order 491 0 12/49 Young et aL 260 41O 6 7 2,758,976 8/5 6 'Barker 252-79 Foam Numbers Fmnum 3V FOREIGN PATENTS 2 11-1 17-12 0 9 1 13 6 1,121,801 1/62. Germany.

Hydroxyethylated OTHER REFERENCES dimer acid, sample 1 1 1 53 M r M 46 Thierfelder et 211.: American Oil Chemists Society l d" 0 ate Tc il i ene nso iu 8 2. 5 2' 5 2O 20 Journal, April 1962, pages 215 217. Stirred 11 111., 5,901 r. .m 0.3 0. 25 0. 15-0. 25 0.2 LEON I B RCO ITZ P Then ad ed a o ymerix zation cataly mgmnn 0.05 0. 1 .12 .0201 13 og-18% V V E amme" 0.25 .1-.- .7. s t i ga'nn 0.15-0.20 0.15 0.15 0.15 DONALD E. CZAJA, Examiner.

Table V:--P0lyurethrin e foams from. hydroxyethylated dimer acids Premix Physical properties I Catalyts. "Water, mt d Triethylene Wt. 7 Load Compres- Foam No. dimer acids Mole diamme, percent Area 1 Compresrequired ign t ratio Wt. percent of polyester shrinkage, Density sion r 25% test, OLE/NCO of polyester percent 1b./ft. modulus, comprespercent of Sample Wt. 1.1.5.1. sion, psi. original No percent height a 2 64 0. 32 0. a 2. 9 3 2. 7 1. 2 0. 6 a 3 82 0. 32 0. 6 3.1 2, 2 0 4 50 a 4 67 0. 32 0. 5 2. 5 8 2. 3 0v 7 0.15 50 5 e3 0. 33 0.3 1.5 16 4.4 13.4 3.5 50 1 69 0. 20 1. 4 2. 9 0 2. 1-2. 2 3. 1 1. 2 44-45 1 69 0.20 1.7 3.9 0 2.2 3.1 1.1 1 74 0. 25 1. 3 2. e 0 2. 3-2. 5 2. 0-2. 3 0. 0 46-50 1 74 0.25 1.6 2.8 0 2.0

B One-shot procedure was used. 

2. POLYESTER URETHANE FOAMS OBTAINED RAPIDLY MIXING ABOUT 35.4 TO 61.0 PARTS BY WEIGHT OF TOLYLENE DIISOCYANATE, ABOUT FROM 0.3 TO 1.7 PARTS BY WEIGHT OF TRIETHYLENEDIAMINE CATALYST, ABOUT FROM 1.5 TO 3.9 PARTS BY WEIGHT OF WATER, AND 100 PARTS BY WEIGHT OF DIMER ACID THAT HAS BEEN ESTERIFIED WITH FROM 1 TO NOT MORE THAN ABOUT 2 MOLE EQUIVALENTS OF EHTYLENE OXIDE, SAID DIMER ACID COMPRISING 3 PARTS OF POLYUNSATURATED VEGETABLE OIL DERIVED C36-DIBASIC ACID AND 1 PART OF SIMILARLY DERIVED C54-TRIBASIC ACID, THE OXYETHYLENATED DIMER ACID REACTANT BEING CHARACTERIZED BY AN ACID NUMBER OF 0-16, A SAPONIFICATION NUMBER OF 172-183, AND A VISCOSITY AT 25*C. OF BETWEEN 36 AND 132 POISES. 